GB1603039A - Aqueous resin composition cross-linkable by oxidation - Google Patents

Description

PATENT SPECIFICATION

C ( 21) Application No 14255/78 ( 22) Filed 12 April 1978 CO ( 31) Convention Application No 52/046 523 ( 32) Filed 22 April 1977 in O ( 33) Japan (JP) C: ( 44) Complete Specification published 18 Nov 1981 ( 51) INT CL 3 C 08 F 291/06, 279/02, 283/00 (C 08 F 283/00, 212/36, 220/20) (C 08 F 291/06, 220/28) ( 52) Index at acceptance C 3 P 154 158 202 203 210 216 220 222 230 234 250 252 256 314 316 318 320 350 354 362 368 370 372 374 384 390 391 394 FC C 3 V ABX C 3 W 114 210 B 212 D 215 B 225 B 304 D 306 D 315 D C 3 Y B 230 B 240 B 243 F 104 F 117 F 530 F 550 H 600 ( 11) 1603039 ( 19 ( 54) AN AQUEOUS RESIN COMPOSITION CROSS-LINKABLE BY OXIDATION ( 71) We, KANSAI PAINT COMPANY LIMITED, a Company of Japan of 365 Kanzaki, Amagasaki-shi, Hyogo-ken, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:-

This invention relates to quick drying aqueous resin compositions which are cross-linkable by oxidation.

Water-soluble resins which are cross-linkable by oxidation heretofore known and used include maleinized drying oils, maleinized semi-drying oils, alkyd resins modified with drying or semi-drying oil fatty acids, maleinized alkyl resins,polybutadiene, epoxy resins modified with drying or semi-drying oil fatty acids and acrylic or vinyl resins modified with drying or semi-drying oil fatty acids Coating compositions prepared from these resins have the drawbacks that the compositions, when applied, form coatings of poor initial hardness and are prone to result in excessive surface drying (i e the phenomenon in which the interior of the coating remains in the semi-liquid state owing to delayed curing) Most preferably such drawbacks can be overcome by the use of resins of increased molecular weight, but the resins of the type described invariably involve limitations on the degree to which they are polymerizable because of their high viscosity and gelling tendency.

Accordingly even when polymerized to the highest possible degree, the resins still need to be improved to fully overcome the foregoing drawbacks Moreover resins of increased molecular weight are not readily soluble in water Although it has been attempted to eliminate the drawbacks by styrenating resins of the oxidation crosslinkable type in the case of those composed of drying oils or alkyd resins, the same difficulties as with the polymerized resins are encountered with the resulting resins.

To provide coatings of improved initial hardness, it is known to use the abovementioned resins in the form of an emulsion However, such emulsions give coatings which are not fully glossy, have reduced toughness due to unequal cross linking and are susceptible to marked skinning leading to popping particularly in the case of high temperature baking.

According to the invention there is provided an aqueous resin composition cross-linkable by oxidation and prepared by dissolving a radicalpolymerizable polyethylenically unsaturated monomer in an aqueous solution comprising from 5 to 85 % by weight of at least one water-soluble resin having a drying oil fatty acid group or semi-drying oil fatty acid group, or neutralized maleinized synthetic petroleum resin having an unsaturated bond and an acid value of from 20 to 350 before neutralisation, and polymerizing the monomer in solution in the presence of an initiator at a temperature above the freezing point of the solvent and below the boiling point thereof, the monomer being used in the ratio by weight of from 1/100 to 2/1 based on the water-soluble resin and/or the neutralized maleinized synthetic petroleum resin, said water-soluble resin being selected from neutralized products of maleinized stand oil, maleinized boiled oil, or other maleinized oil, fatty acid modified alkyd resin, maleinized alkyd resin, fatty acid modified epoxy resin, fatty 2 1,603,039 2acid modified urethane resin, fatty acid modified acrylic resin, fatty acid modified vinyl resin and water-soluble spiran resin.

Our research conducted in order to eliminate the drawbacks of conventional water-soluble resins of the oxidation cross-linkable type has revealed that watersoluble resins having a drying oil fatty acid group or semi-drying oil fatty acid group and neutralized maleinized synthetic petroleum resins having an unsaturated bond when dissolved in water singly or in combination, are in 6 a form resembling microfine balls of threads and that a radical-polymerizable polyfunctional monomer, when polymerized as dissolved in the solution, gives a polymer which is in the form of microfine particles of a gel without causing the gelation of the whole 10 mixture When a mono-functional monomer useful for the preparation of emulsions is used singly for the preparation of aqueous resin compositions of the oxidation cross-linkable type, the functional group contained in the resin will serve as a chain transfer agent against radical polymerization, making it impossible to obtain the desired polymer of increased molecular weight, whereas our research has also is shown that the use of the radical-polymerizable poly-functional monomer eliminates the drawback resulting from the use of the mono-functional monomer.

It is therefore thought that the aqueous resin compositions of this invention have the structure in which the water-soluble resin of the oxidation crosslinkable type extends from the microfine gel-like particles of the polymer formed from the 20 radical-polymerizable poly-functional monomer.

Oils and fatty acids useful for the preparation of the water-soluble resins include, for example, safflower oil, linseed oil, soybean oil, perilla oil, hemp seed oil, grape kernel oil, corn oil, tall oil, cotton seed oil, walnut oil, rubber seed oil and fatty acids of these oils Also usable are tung oil, oiticica oil, dehydrated castor oil, 25 "High-diene" fatty acid and fatty acids of these oils It is preferable to use safflower oil or tall oil which is least likely to adversely affect the reaction Preferably these resins have an oil length of at least about 15, more preferably at least about 25.

When having an oil length of at least about 15, the resins are fully cross-linkable by oxidation as desired The resins are neutralized with a base such as ammonia, 30 amines or alkali metal compounds in the usual manner Amines include primary, secondary and tertiary amines and examples of alkali metal compounds are sodium hydroxide, potassium hydroxide, etc The resins are rendered water-soluble on neutralization.

Examples of useful synthetic petroleum resins having an unsaturated bond are 35 polymers of at least one diene monomer having 4 to 8 carbon atoms, such as butadiene, pentadiene, cyclopentadiene, hexadiene, heptadiene, octadiene, etc; and copolymers of at least 10 wt % of at least one of these dienes and at least one other unsaturated monomer such as an olefin having 2 to 8 carbon atoms, styrene, az-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, chloroprene, and 40 esters of alcohols having I to 18 carbon atoms and acrylic acid or methacrylic acid.

Synthetic petroleum resins useful in this invention also include modified products of the above-mentioned synthetic petroleum resins, such as cyclized, epoxidized and hydrogenated products and hydroxylated products thereof The synthetic petroleum resins can be modified as desired by known methods These synthetic 45 petroleum resins are maleinized and then rendered water-soluble by neutralization for use in this invention The neutralization is conducted by the same manner as described before The maleinization is effected by the known method to such an extent that that maleinized synthetic petroleum resin will have an acid value of 20 to 350, preferably 40 to 250 Resins with an acid value of 20 to 350 have high 50 solubility in water, giving coatings of high resistance to water.

Most preferably as the foregoing resins are those disclosed in Published Unexamined Japanese Patent Application No 126723/1975, because the disclosed resins are prepared by radical polymerization which deactivates specific active groups having a polymerization inhibiting action and therefore permits smooth 55 polymerization of the poly-functional monomer and further because the main chain of the resins is highly compatible with the poly-functional monomer.

Those disclosed resins are neutralized copolymers of (a) a monomer prepared by allowing at least one glycidyl ester of an a-ethylenically unsaturated carboxylic acid to react with at least one unsaturated acid having a non-conjugated double 60 bond, (b) at least one ap-ethylenically unsaturated acid and (c) at least one unsaturated monomer containing substantially no carboxyl group and having a Q value of at least 0 1 as determined by Q-e theory Also preferable are maleinized alkyd resins, maleinized epoxy resins, maleinized acrylic resins and maleinized vinyl resins since the polymerization inhibiting specific active site has been relatively 65 3 1,603,039 3 deactivated in the course of the maleinization.

According to this invention, at least one water-soluble resin having a drying or semi-drying oil fatty acid group or a neutralized maleinized synthetic petroleum resins having an unsaturated bond and an acid value of from 20 to 350 before neutralisation is dissolved in water or in a mixture of water and an organic solvent 5 miscible with water Useful organic solvents are a wide variety of those miscible with water The aqueous solution should have a concentration of about 5 to about % by weight, preferably about 15 to about 70 % by weight.

The radical polymerizable polyethylenically unsaturated monomers useful in this invention must be highly amenable to radical polymerization Examples of useful mono 10 mers are esters of polyhydric alcohols having 2 to 6 functional groups and acrylic acid or methacrylic acid; esters of glycidyl acrylate or glycidyl methacrylate and acrylic acid or methacrylic acid; esters of polycarboxylic acids having 2 to 4 functional groups and glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl 15 methacrylate; esters of poly epoxy compounds having 2 to 4 functional groups and hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid or methacrylic acid; divinylbenzene; adducts of polyisocyanates having 2 to 4 functional groups and hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl 20 methacrylate, acrylic acid or methacrylic acid Also usable are adducts of epoxy polymers of relatively low molecular weight (up to 2,000, preferably up to 500, in number average molecular weight) or compounds containing a hydroxyl and an epoxy group or a hydroxyl and a carboxyl group and acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl, 25 acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate Further usable are adducts prepared from the hydroxyl containing monomers mentioned above and methylolated melamine, urea or ethyl silicate by an ether exchange reaction Preferable among these radical-polymerizable polyfunctional monomers are the esters of polyhydric alcohols having 2 to 6 functional 30 groups and acrylic acid or methacrylic acid; esters of glycidyl acrylate or glycidyl methacrylate and acrylic acid or methacrylic acid; esters of polycarboxylic acid having 2 to 4 functional groups and glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate; esters of polyepoxy compounds having 2 to 4 35 functional groups and acrylic acid or methacrylic acid; and divinylbenzene.

According to this invention it is necessary to use at least one of the monomers given above These monomers are usable conjointly with a radicalpolymerizable mono-ethylenically unsaturated monomer The mono-ethylenically unsaturated monomer is used in an amount of up to 80 % by weight, preferably up to 40 % by 40 weight, based on the combined amount of the monomers used If more than 80 % by weight of the mono-ethylenically unsaturated monomer is used, low molecular weight polymers which have non-fixing property on the water-soluble resins will be produced in the polymerization system, and, consequently, a solution thus prepared will become so close to an emulsion that the low molecular weight 45 polymers are prone to flocculate in the system and result in even large particles.

Examples of useful mono-ethylenically unsaturated monomers are the esters represented by the formula CH 2 =C(R 1)COOR 2 wherein R 1 is hydrogen or CH 3, and R 2 is alkyl having 1 to 26 carbon atoms; esters represented by the formula CH 2 =C(R 1)COOR 3 50 wherein R 1 is as defined above, and R 3 is CH CH-CH 2, CH 2 CH(OH)CH 2 OCOR 4, (CH 2 CH 2 O)n Rs, lCH 2 CH(CH 3)Oln Rs, CH 2 CH(CH 3)OH or CH 2 CH 2 CH 2 OH, 55 R 4 is hydrogen or alkyl having I to 25 carbon atoms, Rs is hydrogen or alkyl having 1 to 8 carbon atoms, and N is an integer of 1 to 8; and styrene, vinyltoluene, acmethylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, a vinyl ester of synthetic tertiary carboxylic acid, having the proposed general formula:

R, R 7-C-COCH=CH 2 R 8 wherein R, R, and R are alkyl and at least one of them is CH 3 (sold commercially 5 as VEOVA "Registered Trade Mark"), adducts of glycidyl acrylate or methacrylate and fatty acids, acrylic acid, methacrylic acid; carboxylic acid amides represented by the formula CH 2 =C(Rg)CONH Ro wherein R 9 is hydrogen or CH 3 and Ro is hydrogen, -CH 2 OH or-CH 2 OC 4,H 9 N-methy lacrylamide, Nethylacrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, vinyl pyridine, 10 vinyl pyrrolidone, among which the esters represented by the formula CH 2 =C(R)COOR 2; esters represented by the formula CH 2 =C(R,)COOR 3; and styrene, vinyltoluene, a-methylstyrene, methacrylonitrile, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, Nbutoxymethyl acrylamide, vinyl acetate, "VEOVA", adducts of glycidyl acrylate or 15 methacrylate and fatty acids, acrylic acid and methacrylic acid are preferable.

According to this invention, the radical-polymerizable poly-functional monomer is used in the ratio by weight of from 1/100 to 2/1, preferably from about 3/100 to about 1/1, based on the water-soluble resin and/or the neutralized maleate of synthetic, petroleum resin If this ratio is less than 1/100, the expected effect of 20 poly-functional monomers is not distinctly observed, whereas if it is more than 2/1, the resulting composition is very likely to have the properties of an emulsion, hence undesirable.

The radical-polymerizable monomer is polymerized in the presence of an initiator at a temperature of above the freezing point of the solvent and below the 25 boiling point thereof, preferably 0 to 100 C For this reaction any radical producing initiators are usable such as gamma rays and like ionizing radiations, peroxides and azo-type initiators The concentration of the reaction system is usually about 10 to about 60 %' by weight.

The aqueous resin compositions of the oxidation cross-linkable type according 30 to this invention may be used in mixed systems with other known water soluble resins as well as the singly and are useful as coating compositions and also for a wide range of applications as processing resins For coating purposes, pigments and other additives may be incorporated into the compositions in the usual manner.

For a better understanding of the present invention, examples and comparison 35 examples will be given below in which the parts and percentages are all by weight unless otherwise specified.

Example 1.

A monomer prepared by the addition reaction of glycidyl methacrylate with safflower oil fatty acid, styrene, n-butyl methacrylate and acrylic acid are mixed 40 together in the ratio by weight of 60/14/14/12 The mixture is subjected to radical polymerization in butyl "Cellosolve" (Registered Trade Mark) (ethylene glycol mono-butyl ether) to obtain a water soluble resin A which is crosslinkable by oxidation and which has an oil length of 40, an acid value of 80 and a peak molecular weight of about 7,000 to about 8,000 The resin is neutralized with an 45 equivalent of triethylamine and then formulated into an aqueous solution containing butyl "Cellosolve" The solution is placed into a four-necked flask and heated to 80 C with stirring in a nitrogen gas atmosphere To the solution is added 1,6-hexanediol diacrylate (containing azobisdimethylvaleronitrile dissolved therein in a quantity corresponding to 10 % of the monomer quantity) in amount 50 corresponding to 10 % of the amount of the water-soluble resin to prepare a transparent solution The solution is maintained at 80 C for 7 hours to obtain an aqueous resin composition of the oxidation cross-linkable type.

Table I shows the properties of the composition and Table 2 those of the coating formed from the composition The properties of the composition are 55 expressed in terms of the ratio between the viscosities measured by a Brookfield viscometer at two different speeds of rotation Coated panels are prepared by 1,603,039 1,603,039 5 applying the composition (incorporating 0 05 % Co, 0 05 % Mn and, 0 15 % Pb as respectively metal content and 0 5 % Active-8 (drier manufactured by R T Vanderbilt Co, U S A) in the form of a drier) to a polished mild steel panel by a bar coater to a thickness of 25 of 30 u and baking the panel at 801 C for 20 minutes or drying the panel at 200 C for 7 days The panels are tested for the properties of the 5 coating The panel tested for the gloss of the coating is prepared in the same manner as above except that the composition contains 80 PHR of titanium white.

Examples 2 to 5 and Comparison Examples 1 and 2 Aqueous resin compositions are prepared in the same manner as in Example 1 except that the conditions are as listed in Table 1 Table 1 also shows the properties 10 of the compositions, and Table 2 the properties of the coatings prepared from the compositions.

TABLE 1

Conditions for the preparation of water-soluble resin Properties 5 Water Amount of monomer Amount of Solids (%) 4 soluble (in PHR, based on butyl "Cello Viscosity ratio Example resin water soluble resin) solve" ( PHR) Calcd Found ( 6 rpm/30 rpm/ Appearance Ex 1 A 1,6-H D D A 1 10 45,5 37 6 37 5 1 0 Transparent 2 A 1,6-H D D A 20 41 7 29 0 29 6 1 0,, 3 A 1,6-H D D A 50 33 3 36 3 37 0 1 2 Slightly white 4 A Divinylbenzene 5 47 7 34 7 350 1 Transparent A N K ESTER 2 10 45 5 3 7 6 37 4 1 1,, Comp Ex 1 A None 50 0 34 8 0 95,, 2 A n-B M A 3 10 45 5 37 6 36 ? 1 0,, Notes: 1 1,6-Hexanediol diacrylate.

2 Pentaerythritol triacrylate, product of Shin-Nakamura Chemical Co, Ltd, Japan.

3 n-Butyl methacrylate.

4 Comparison between the two values indicates that the monomer has been polymerized.

As this value increases, the composition becomes thixotropic and has a closer resemblance to an amulsion.

0 b-I a O i j TABLE 2

Baking at 80 C for 2 O min Drying at 20 'C for 7 days Variations in pencil hardness Gel Gel Pencil Water fraction 1 St 2 nd 4 th 7 th Water fraction Gloss Example hardness resistance ratio day day day day resistance ratio ( 60 C) Ex 1 4 B b 60 9 6 B< 3 B 2 B B d 65 3 82 2 3 B a 66 7 6 B< B B B d 68 3 77 3 B a 72 6 6 B B B B a 70 0 65 4 4 B b 54 4 6 B< 2 B 2 B B d 67 2 83 4 B a 63 6 6 B 3 B B B d 68 4 80 Comp Ex 1 6 B< b 40 0 6 B< SB 4 B 4 B d 60 0 83 , 2 6 B< b 45 0 6 B< 4 B 4 B 3 B d 63 5 80 Note: Test methods and evaluation procedures are cited at the end of the specification.

o L/o Example 6 and Comparison Example 3 269 g of 1,1,1-trimethylol propane, 213 g of phthalic anhydride, 3 8 g of trimellitic anhydride, 402 g of safflower oil fatty acid, 156 g of benzoic acid, 2 g of di-n-butyl tin oxide and 50 g of xylene are placed into a 2-litre fournecked flask and heated at 2300 C in a nitrogen atmosphere for 4 hours to obtain a fatty acid 5 modified alkyd resin having an acid value of 13 3 96 g of maleic anhydride is added to the alkyd resin solution and the mixture is maleinized at 1900 C for 3 hours The excess maleic anhydride and xylene are removed from the maleinized product solution under reduced pressure The product is subjected to a ring cleavage reaction by adding 22 g of water, thus the maleinized alkyd resin B having a total 10 acid value of 71 is obtained The resin is neutralized with an equivalent of triethylamine and formulated into an aqueous solution with addition of butyl "Cellosolve" In the same manner as in Example 1, the polyu-functional monomer listed in Table 3 is added to the solution and polymerized to prepare an aqueous resin composition of the oxidation cross-linkable type The composition is slightly 15 hazy at 800 C but is transparent at room temperature Table 3 shows the properties of the composition, and Table 4 those of the coatings prepared therefrom.

Example 7.

548 g of phthalic anhydride, 710 g of pentaerythritol, 1704 g of linseed oil fatty acid 779 g of benzoic acid, 7 g of di-n-butyl tin oxide and 150 g of xylene are placed 20 into a 5-litre four-necked flask and heated at 235 C in a nitrogen atmosphere for 7 hours to obtain a fatty acid modified alkyd resin having an acid value of 5 5 325 g of maleic anhydride is added to the aikyd resin solution and the mixture is maleinized at 190 C for 4 hours The excess maleic anhydride and xylene are removed from the maleinized product solution under reduced pressure The 25 product is subjected to a ring cleavage reaction by adding 90 g of water, thus the maleinized alkyd resin C having a total acid value of 80 3 is obtained The resin is neutralized with an equivalent of triethylamine and formulated into an aqueous solution with addition of butyl "Cellosolve" In the same manner as in Example I, the poly-functional monomer listed in Table 3 is added to the solution and 30 polymerized to prepare an aqueous resin composition of the oxidation crosslinkable type The composition is tested for properties with the results given in Tables 3 and 4.

Examples 8 to 10 and Comparison Examples 4 and 5 35 Aqueous resin compositions are prepared in the same manner as in Example 1 except that the conditions were as listed in Table 3 The compositions are tested for properties with the results given in Tables 3 and 4.

1,603,039 TABLE 3

Conditions for the preparation of water-soluble resin Properties 5 Water Amount of monomer Amount of Solids (%) 4 soluble (in PHR, based on butyl "Cello Viscosity ratio Example resin water soluble resin) solve" (PHR) Calcd Found ( 6 rpm/30 rpm) Appearance Ex 6 B 1,6-11 D D A 1 0 63 31 7 30 9 1 0 Transparent Comp Ex 3 B None 63 3 4 9 0 98,, Ex 7 C 1,6-H D D A 10 30 4 34 4 33 1 0 95,, 8 C,, 20 27 8 3 5 3 33 2 1 0,, 9 C Divinylbenzene 5 31 9 33 0 32 5 1 0,, C N K ESTER 10 30 4 34 4 34 ' 0 1 1 Comp Ex 4 C None 41 2 3 2 5 1 O,, C n-B M A 10 30 4 34 4 32 0 1 0,, 0 \To TABLE 4

Baking at 80 C for 20 min Drying at 20 C for 7 days Variations in pencil hardness Ge l Gel Pencil Water fraction 1st 2nd 4th 7th Water fraction Gloss Example hardness resistance ratio day day day day resistance ratio ( 60 ) Ex 6 4 B b 63 8 6 B< 3 B 3 B B c 57 6 87 Comp Ex 3 6 B< d 42 3 6 B< 4 B 3 B 2 B c 49 1 90 Ex 7 6 B b 50 9 6 B 4 B 3 B 2 B c 55 0 89 8 4 B a 52 1 6 B 4 B 3 B B b 57 9 87 9 6 B b 40 2 6 B 4 B 3 B B d 43 2 90 Slight yel low6 B b 42 8 6 B 4 B 2 B 2 B c 47 3 88 ing Comp Ex 4 ' 6 B< d 2 2 8 6 B< 6 B 4 B 3 B d 35 1 91 , 5 6 B< d 25 5 6 B< 6 B 4 B 3 B d 39 2 93 0 C \.0 1 Test methods and evaluation procedures Pencil hardness:

The coating is scratched with pencils ("MITSUBISHI UNI," product of Mitsubishi Pencil Co, Japan) of varying hardnesses to determine the pencil of the highest hardness producing no scratches in the coating The hardness of the coating 5 is expressed in terms of the pencil hardness thus determined.

Water resistance:

The coating panel is immersed in water at 20 C for 24 hours and thereafter checked for changes produced in the coating The results are evaluated according to the following criteria: 10 a: no defect (Good) b: slight whitening (Fair) c: whitening (Poor) d:whitening with reduced gloss (Bad) Gel fraction ratio:

Calculated from the difference in the weight of the coating resulting from the 15 extraction of the coating with acetone.

Claims (14)

WHAT WE CLAIM IS:-

1 An aqueous resin composition cross-linkable by oxidation and prepared by dissolving a radical-polymerizable poly-ethylenically unsaturated monomer in an aqueous solution comprising from 5 to 85 % by weight of at least one water-soluble 20 resin having a drying oil fatty acid group of semi-drying oil fatty acid group, or neutralized maleinized synthetic petroleum resin having an unsaturated bond and an acid value of from 20 to 350 before neutralisation, and polymerizing the monomer in solution in the presence of an initiator at a temperature above the freezing point of the solvent and below the boiling point thereof, the monomer 25 being used in the ratio by weight of from 1/100 to 2/1 based on the watersoluble resin and/or the neutralized maleinized synthetic petroleum resin, said water-soluble resin being selected from neutralized products of maleinized stand oil, maleinized boil oil, or other maleinized oil, fatty acid modified alkyd resin, maleinized alkyd resin, fatty acid and modified epoxy resin, fatty acid modified urethane resin, fatty 30 acid modified acrylic resin, fatty acid modified vinyl resin and watersoluble spiran resin.

2 An aqueous resin composition cross-linkable by oxidation according to claim I in which the monomer is used in the ratio by weight of from 3/100 to about 1/1 based on the water-soluble resin and/or the neutralized maleinized synthetic 35 petroleum resin.

3 An aqueous resin composition cross-linkable by oxidation according to claim I in which a radical-polymerizable mono-ethylenically unsaturated monomer is used conjointly with the radical-polymerizable poly-ethylenically unsaturated m onomer in an amount of up to 80 O by weight based on the combined amount of 40 the monomers used.

4 An aqueous resin composition cross-linkable by oxidation according to claim 3 in which said amount of the radical-polymerizable monoethylenically unsaturated monomer is up to 40 wt %' based on the combined amount of the monomers used 45 An aqueous resin composition cross-linkable by oxidation according to claim 4 in which said radical-polymerizable mono-ethylenically unsaturated monomer is at least one ester represented by the formula CH 2 =C(R,)COOR 2 wherein R, is hydrogen or CH 3, and R 2 is alkyl having 1 to 26 carbon atoms; an ester represented by the formula CH 2 =C(R,)COO Ra wherein R, is as defined 50 above, and R 3 is CH CH-CH 2 ' 0 CH 2 CH(OH)CH 1 OCOR 4, (CH 2 CH 20),R 5, l CH 2 CH(CH 3)O 1)R,' CH 2 CH(CH 3)OH

5 5 or CH 2 CH 2 CHOH, R 4 is hydrogen or alkyl having 1 to 25 carbon atoms, R 5 is 1,603,039 hydrogen or alkyl having I to 8 carbon atoms, and N is an integer of 1 to 8; and styrene, vinyltoluene, a-methyl styrene, acrylonitrile, methacrylonitrile, vinyl acetate, a vinyl ester of synthetic tertiary carboxylic acid, having the proposed general formula:

R 6 R 7-C-COCH=CH 2 5 R 8 wherein R 6, R 7 and R 8 are alkyl and at least one of them is CH 3, adducts of glycidyl acrylate or methacrylate and fatty acids, acrylic acid, methacrylic acid; carboxylic acid amides represented by the formula CH 2 =C(Rg)CONHR 10 wherein R is hydrogen or CH 3 and R 10 is hydrogen, -CH 2 OH or CH 2 OC 4 Hg, N-methyl acrylamide, N-ethyl acrylamide, dimethylaminoethyl methacrylate, 10 diethylaminoethyl methacrylate, vinyl pyridine and vinyl pyrrolidone.

6 An aqueous resin composition cross-linkable by oxidation according to any preceding claim in which said polymerization is conducted at a temperature of from O C to 100 C.

7 An aqueous composition cross-linkable by oxidation according to any 15 preceding claim in which said radical-polymerizable poly-ethylenically unsaturated monomer is selected from esters of polyhydric alcohols having 2 to 6 functional groups and acrylic acid or methacrylic acid: ester of glycidyl acrylate or glycidyl methacrylate and acrylic acid or methacrylic acid; esters of polycarboxylic acids having 2 to 4 functional groups and glycidyl acrylate, glycidyl methacrylate, 20 hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate; esters of polyepoxy compounds having 2 to 4 functional groups and hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid or methacrylic acid; adducts of polyisocyanates having 2 to 4 functional groups and hydroxyethyl 25 acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid or methacrylic acid; divinylbenzene; adducts of epoxy polymers of relatively low molecular weight (up to 2,000, in number average molecular weight) or compunds containing a hydroxyl and an epoxy group or a hydroxyl group and a carboxyl group and acrylic acid, methacrylic acid, glycidyl 30 acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxypropyl methacrylate; adducts prepared from the hydroxyl-containing monomers mentioned above and methylolated melamine, urea or ethyl silicate by ether exchange reaction.

8 An aqueous resin composition cross-linkable by oxidation according to any 35 preceding claim, in which said neutralized product is derived from safflower oil, linseed oil, soybean oil, perilla oil, hemp seed oil, grape kernel oil, corn oil, tall oil, cotton seed oil, walnut oil, rubber seed oil, tung oil, oiticica oil, dehydrated caster oil and fatty acids of these oils.

9 An aqueous resin composition cross-linkable by oxidation according to any 40 preceding claim, in which said water-soluble resin has an oil length of at least 15.

An aqueous resin composition cross-linkable by oxidation according to any preceding claim, in which said maleinized synthetic petroleum resin is selected from polymers of at least one diene monomer having 4 to 8 carbon atoms and copolymers of at least

10 wt,' of at least one of the above dienes and at least one 45 other unsaturated monomer.

11 An aqueous resin composition cross-linkable by oxidation according to claim 10 in which said diene is selected from butadiene, pentadiene, cyclopentadiene, hexadiene, heptadiene and octadiene.

12 An aqueous resin composition cross-linkable by oxidation according to 50 claim 10 or claim 11 in which said unsaturated monomer is selected from olefins having 2 to 8 carbon atoms, styrene, a-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, chloroprene, and esters of alcohols having 1 to 18 carbon atoms and acrylic acid or methacrylic acid.

13 An aqueous resin composition cross-linkable by oxidation according to any 55 preceding claim, in which said synthetic petroleum resin is selected from the cyclized, epoxidized and hydrogenated products of a synthetic petroleum resin and hydroxides thereof.

14 An aqueous resin composition cross-linkable by oxidation as claimed in claim I substantially as described herein with reference to any one of the Examples 60 1,603,039 13 1,603,039 1 3 Agents for the Applicants:

WILSON, GUNN & ELLIS Chartered Patent Agents 41 Royal Exchange Manchester, M 2 7 DB Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1981.

Published by the Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.